Cleaning formulation for removing residues on surfaces

ABSTRACT

This disclosure relates to a cleaning composition that contains 1) at least one redox agent; 2) at least one first chelating agent, the first chelating agent being a polyaminopolycarboxylic acid; 3) at least one second chelating agent different from the first chelating agent, the second chelating agent containing at least two nitrogen-containing groups; 4) at least one metal corrosion inhibitor, the metal corrosion inhibitor being a substituted or unsubstituted benzotriazole; 5) at least one organic solvent selected from the group consisting of water soluble alcohols, water soluble ketones, water soluble esters, and water soluble ethers; 6) water; and 7) optionally, at least one pH adjusting agent, the pH adjusting agent being a base free of a metal ion. This disclosure also relates to a method of using the above composition for cleaning a semiconductor substrate.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims priority to U.S. Provisional ApplicationSer. No. 61/936,999, filed on Feb. 7, 2014, and U.S. ProvisionalApplication Ser. No. 61/912,697, filed on Dec. 6, 2013, the contents ofwhich are hereby incorporated by reference in its entirety.

BACKGROUND

1. Field of the Disclosure

The present disclosure relates to a novel cleaning composition forsemiconductor substrates and a method of cleaning semiconductorsubstrates. More particularly, the present disclosure relates to acleaning composition for removing plasma etch residues formed onsemiconductor substrates after plasma etching of metal layers ordielectric material layers deposited on the substrates and the removalof residues left on the substrates after bulk resist removal via aplasma ashing process.

2. Discussion of the Background Art

In the manufacture of integrated circuit devices, photoresists are usedas an intermediate mask for transferring the original mask pattern of areticle onto the wafer substrate by means of a series ofphotolithography and plasma etching steps. One of the essential steps inthe integrated circuit device manufacturing process is the removal ofthe patterned photoresist films from the wafer substrate. In general,this step is carried out by one of two methods.

One method involves a wet stripping step in which thephotoresist-covered substrate is brought into contact with a photoresiststripper solution that consists primarily of an organic solvent and anamine. However, stripper solutions cannot completely and reliably removethe photoresist films, especially if the photoresist films have beenexposed to UV radiation and plasma treatments during fabrication. Somephotoresist films become highly crosslinked by such treatments and aremore difficult to dissolve in the stripper solution. In addition, thechemicals used in these conventional wet-stripping methods are sometimesineffective for removing inorganic or organometallic residual materialsformed during the plasma etching of metal or oxide layers withhalogen-containing gases.

An alternative method of removing a photoresist film involves exposing aphotoresist-coated wafer to oxygen-based plasma in order to burn theresist film from the substrate in a process known as plasma ashing.However, plasma ashing is also not fully effective in removing theplasma etching by-products noted above. Instead, removal of these plasmaetch by-products is typically accomplished by subsequently exposing theprocessed metal and dielectric thin films to certain cleaning solutions.

Metal substrates are generally susceptible to corrosion. For example,substrates such as aluminum, copper, aluminum-copper alloy, tungstennitride, tungsten (W), cobalt (Co), titanium oxide, other metals andmetal nitrides, will readily corrode and dielectrics [ILD, ULK] can etchby using conventional cleaning chemistries. In addition the amount ofcorrosion tolerated by the integrated circuit device manufacturers isgetting smaller and smaller as the device geometries shrink.

At the same time as residues become harder to remove and corrosion mustbe controlled to ever lower levels, cleaning solutions must be safe touse and environmentally friendly.

Therefore, the cleaning solution should be effective for removing theplasma etch and plasma ash residues and must also be non-corrosive toall exposed substrate materials.

SUMMARY OF THE DISCLOSURE

The present disclosure is directed to a non-corrosive cleaningcomposition that is useful primarily for removing residues (e.g., plasmaetch and/or plasma ashing residues) from a semiconductor substrate as anintermediate step in a multistep manufacturing process. These residuesinclude a range of relatively insoluble mixtures of organic compoundslike residual photoresist, organometallic compounds, metal oxides whichare formed as reaction by-products from exposed metals such as aluminum,aluminum/copper alloy, copper, titanium, tantalum, tungsten, cobalt,metal nitrides such as titanium and tungsten nitrides, and othermaterials. An advantage of the cleaning composition described herein isthat it can clean a broad range of residues encountered and be generallynon-corrosive to exposed substrate materials (e.g., exposed metals suchas aluminum, aluminum/copper alloy, copper, titanium, tantalum,tungsten, cobalt, and metal nitrides such as titanium and tungstennitrides).

In one aspect, the present disclosure features a cleaning compositioncontaining 1) at least one redox agent, 2) at least one first chelatingagent, the first chelating agent being a polyaminopolycarboxylic acid,3) at least one second chelating agent different from the firstchelating agent, the second chelating agent containing at least twonitrogen-containing groups, 4) at least one metal corrosion inhibitor,the metal corrosion inhibitor being a substituted or unsubstitutedbenzotriazole, 5) at least one organic solvent selected from the groupconsisting of water soluble alcohols, water soluble ketones, watersoluble esters, and water soluble ethers, 6) water, and 7) optionally,at least one pH adjusting agent, the pH adjusting agent being a basefree of a metal ion. In some embodiments, the pH of the cleaningcomposition is between about 6 and about 11 (e.g., between about 6 andabout 9.5). In some embodiments, the cleaning composition is a uniformsolution.

For example, the cleaning composition can include:

-   -   1) about 0.5% to about 20% by weight of at least one redox        agent;    -   2) about 0.01% to about 1% by weight of at least one first        chelating agent;    -   3) about 0.01% to about 1.8% by weight of at least one second        chelating agent;    -   4) about 0.05% to about 1% by weight of at least one metal        corrosion inhibitor;    -   5) about 1% to about 30% by weight of at least one organic        solvent;    -   6) about 78% to about 98% water, and    -   7) optionally, at least one pH adjusting agent.

The present disclosure is also directed to a method of cleaning residuesfrom a semiconductor substrate. The method includes contacting asemiconductor substrate containing post etch residues and/or post ashresidues with a cleaning composition described herein. For example, themethod can include the steps of:

-   -   (A) providing a semiconductor substrate containing post etch        and/or post ash residues;    -   (B) contacting said semiconductor substrate with a cleaning        composition described herein;    -   (C) rinsing said semiconductor substrate with a suitable rinse        solvent; and    -   (D) optionally, drying said semiconductor substrate by any means        that removes the rinse solvent and does not compromise the        integrity of said semiconductor substrate.

DETAILED DESCRIPTION OF THE DISCLOSURE

As defined herein, unless otherwise noted, all percentages expressedshould be understood to be percentages by weight to the total weight ofthe cleaning composition. Unless otherwise noted, ambient temperature isdefined to be between about 16 and about 27 degrees Celsius (° C.).

As defined herein, a “water-soluble” substance (e.g., a water-solublealcohol, ketone, ester, or ether) refers to a substance having asolubility of at least 5% by weight in water at 25° C.

One embodiment of the present disclosure is directed to a non-corrosivecleaning composition comprising:

-   -   1) about 0.5% to about 20% by weight of at least one redox        agent;    -   2) about 0.01% to about 1% by weight of at least one first        chelating agent, the first chelating agent being a        polyaminopolycarboxylic acid;    -   3) about 0.01% to about 1.8% by weight of at least one second        chelating agent different from the first chelating agent, the        second chelating agent containing at least two        nitrogen-containing groups,    -   4) about 0.05% to about 1% by weight of at least one metal        corrosion inhibitor selected from the group consisting of        substituted and unsubstituted benzotriazoles;    -   5)) about 1% to about 30% by weight of at least one organic        solvent selected from the group consisting of water soluble        alcohols, water soluble ketones, water soluble esters, and water        soluble ethers;    -   6) about 78% to about 98% water, and    -   7) optionally, at least one at least one pH adjusting agent, the        pH adjusting agent being a base free of a metal ion and        adjusting the pH of the cleaning composition to between about 6        and about 9.5.

The compositions of this disclosure contain at least one redox agent,which aids in the dissolution of residues on the semiconductor surfacesuch as photoresist residues, metal residues, and metal oxide residues.As used herein, the term “redox agent” refers to a compound that caninduce an oxidation and a reduction in a semiconductor cleaning process.An example of a suitable redox agent is hydroxylamine. In someembodiments, the redox agent does not include a peroxide (e.g., hydrogenperoxide).

In some embodiments, the compositions of this disclosure include atleast about 0.5% by weight (e.g., at least about 1% by weight, at leastabout 2% by weight, at least about 3% by weight, or at least about 5% byweight) and/or at most about 20% by weight (e.g., at most about 17% byweight, at most about 15% by weight, at most about 12% by weight, or atmost about 10% by weight) of the redox agent.

The compositions of this disclosure contain at least one first chelatingagent, which can be a polyaminopolycarboxylic acid. For the purposes ofthis disclosure, a polyaminopolycarboxylic acid refers to a compoundwith a plurality of amino groups and a plurality of carboxylic acidgroups. Suitable classes of polyaminopolycarboxylic acid chelatingagents include, but are not limited to mono- or polyalkylene polyaminepolycarboxylic acids, polyaminoalkane polycarboxylic acids,polyaminoalkanol polycarboxylic acids, and hydroxyalkylether polyaminepolycarboxylic acids.

Suitable polyaminopolycarboxylic acid chelating agents include, but arenot limited to, butylenediaminetetraacetic acid,diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetrapropionicacid, triethylenetetraminehexaacetic acid,1,3-diamino-2-hydroxypropane-N,N,N′,N′-tetraacetic acid,propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid(EDTA), trans-1,2-diaminocyclohexane tetraacetic acid, ethylendiaminediacetic acid, ethylendiamine dipropionic acid,1,6-hexamethylene-diamine-N,N,N′,N′-tetraacetic acid,N,N-bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid,diaminopropane tetraacetic acid,1,4,7,10-tetraazacyclododecane-tetraacetic acid, diaminopropanoltetraacetic acid, and (hydroxyethyl)ethylenediaminetriacetic acid.

In some embodiments, the compositions of this disclosure include atleast about 0.01% by weight (e.g., at least about 0.1% by weight, atleast about 0.2% by weight or at least about 0.3% by weight) and/or atmost about 1% by weight (e.g., at most about 0.7% by weight, at mostabout 0.6% by weight or at most about 0.5% by weight) of thepolyaminopolycarboxylic acid chelating agent.

In general, the compositions of this disclosure can contain at least onesecond chelating agent having at least 2 nitrogen containing groups(e.g., nitrogen containing groups with chelating ability). Examples ofsuitable nitrogen containing groups include primary amino, secondaryamino, imidazolyl, triazolyl, benzotriazolyl, piperazinyl, pyrolyl,pyrrolidinyl, pyrazolyl, piperidinyl, guanidinyl, biguanidinyl,carbazatyl, hydrazidyl, semicarbazidyl, and aminoguanidinyl. Compoundswith combinations of any two or more of these groups are contemplated.The second chelating agent having at least 2 nitrogen containing groupsmay be added as the compound itself, or as its neutralized salt. In someembodiments, the second chelating agent is optional in the compositionsof this disclosure.

For the purposes of this disclosure, the polyaminopolycarboxylic acidsare excluded from the second chelating agent. In other words, the secondchelating agent is different from the first chelating agent. However, insome embodiments, the second chelating agent may include one or morecarboxylic acid groups.

For example, the second chelating agent can be a monocarboxylic acidcompound containing a primary or secondary amino group and at least oneadditional nitrogen-containing basic group. For the purpose of thisdisclosure, the required primary or secondary amino group is notdirectly bonded to nor part of the additional nitrogen containing basicgroup (e.g. NH₂, H₂NC(═X), or H₂NNHC(═X), where X═O, S, or NR, R being Hor C₁-C₄ alkyl). In other words, NH₂NH—, H₂NC(═X)NH—, or H₂NNHC(═X)NH—are not considered the primary or secondary amino group within thisdisclosure. Thus, a monocarboxylic acid containing such a basic grouponly (e.g., NH₂NH—, H₂NC(═X)NH—, or H₂NNHC(═X)NH—) does not include aprimary or secondary amino group and is therefore excluded from themonocarboxylic acid compound containing a primary or secondary aminogroup and at least one additional nitrogen-containing basic groupdescribed in this disclosure. Examples of such excluded monocarboxylicacids include guanidinoacetic acid and 4-guanidinobutyric acid.

Suitable classes of monocarboxylic acid compound containing a primary orsecondary amino group and at least one additional nitrogen-containingbasic group are those monocarboxylic acid compounds which contain aprimary or secondary amino group and at least one of the followingnitrogen-containing basic groups selected from the group consisting ofimidazolyl, triazolyl, benzotriazolyl, piperazinyl, pyrolyl,pyrrolidinyl, pyrazolyl, piperidinyl, guanidinyl, carbazatyl,hydrazidyl, semicarbazidyl, aminoguanidinyl, primary amino (e.g., C₁-C₁₀primary amino), and secondary amino (e.g., C₁-C₁₀ secondary amino).These groups may be further substituted with substituents, e.g. loweralkyl groups, except for the secondary amino group.

In some embodiments of the disclosure, the at least one monocarboxylicacid compound containing a primary or secondary amino group and at leastone additional nitrogen-containing basic group is selected from thecompounds described by the generic Structure (I):(R³NH)C(R¹)(R²)CO₂H  (I),in which each of R¹ and R², independently, is a hydrogen atom, C₁-C₄alkyl, or a group (e.g., a C₁-C₁₀ group) having at least onenitrogen-containing basic group; and R³ is a hydrogen atom, C₁-C₁₀alkyl, or a group (e.g., a C₁-C₁₀ group) having at least onenitrogen-containing basic group; in which at least one of R¹, R², and R³is a group having at least one nitrogen-containing basic group.

In some embodiments, R¹ can be a group having at least onenitrogen-containing basic group, in which the group having at least onenitrogen-containing basic group is C₁-C₁₀ alkyl substituted by amino,guanidinyl, or imidazolyl and optionally further substituted by OH. Insuch embodiments, R² can be H or C₁-C₁₀ alkyl and R³ can be H, C₁-C₁₀alkyl, or a group having at least one nitrogen-containing basic group,in which the group having at least one nitrogen-containing basic groupis C₁-C₁₀ alkyl optionally substituted by amino, guanidinyl, orimidazolyl and optionally further substituted by OH.

In some embodiments, R³ can be a group having at least onenitrogen-containing basic group, in which the group having at least onenitrogen-containing basic group is C₁-C₁₀ alkyl substituted by amino,guanidinyl, or imidazolyl and optionally further substituted by OH. Insuch embodiments, each of R¹ and R², independently, can be H or C₁-C₄alkyl.

In some embodiments of the disclosure, the at least one monocarboxylicacid compound containing a primary or secondary amino group and at leastone additional nitrogen-containing basic group is selected from thecompounds of Structure (I) described above, where R¹ is a group havingat least one nitrogen-containing basic group and each of R² and R³ is ahydrogen atom. Examples of compounds having this structure include, butare not limited to, lysine, 2,3-diaminobutyric acid, 2,4-diaminobutyricacid, ornithine, 2,3-diaminopropionic acid, 2,6-diaminoheptanoic acid,4-methyl lysine, 3-methyl lysine, 5-hydroxylysine, 3-methyl-L-arginine,arginine, homoarginine, N⁵-monomethyl-L-arginine,N⁵-[imino(methylamino)methyl]-D-ornithine, canavanine, and histidine.

In some embodiments of the disclosure, the at least one monocarboxylicacid compound containing a primary or secondary amino group and at leastone additional nitrogen-containing basic group is selected from thecompounds described by Structure (I) described above, where each of R¹and R² is a hydrogen atom, and R³ is a C₁-C₁₀ group containing a grouphaving at least one nitrogen-containing basic group. Examples ofcompounds having this structure include, but are not limited to,N-(2-aminoethyl)glycine and N-(2-aminopropyl)glycine.

In some embodiments of the disclosure, the at least one monocarboxylicacid compound containing a primary or secondary amino group and at leastone additional nitrogen-containing basic group is selected from thecompounds described by Structure (I) described above, where R¹ is agroup having at least one nitrogen-containing basic group, R² is ahydrogen atom, and R³ is a C₁-C₁₀ alkyl group. Examples of compoundshaving this structure include, but are not limited to, N2-methyl lysine,and N2-methyl-L-Arginine.

In some embodiments of the disclosure, the at least one monocarboxylicacid compound containing a primary or secondary amino group and at leastone additional nitrogen-containing basic group is selected from themonocarboxylic acid compounds described by Structure (I) describedabove, where R¹ is a group having at least one nitrogen-containing basicgroup, R² is a hydrogen atom, and R³ is a group having at least onenitrogen-containing basic group. Examples of compounds having thisstructure includes, but are not limited to,N²-(2-aminoethyl)-D-arginine, and N²-(2-aminoethyl)-L-arginine.

In some embodiments of the disclosure, the at least one monocarboxylicacid compound containing a primary or secondary amino group and at leastone additional nitrogen-containing basic group is selected from themonocarboxylic acid compounds described by Structure (I) describedabove, where R¹ is a C₁-C₄ alkyl, R² is a group having at least onenitrogen-containing basic group, and R³ is a hydrogen atom. Examples ofcompounds having this structure include, but are not limited to,2-methyllysine and 2-methyl-L-arginine.

In some embodiments of the disclosure, the at least one monocarboxylicacid compound containing a primary or secondary amino group and at leastone additional nitrogen-containing basic group is selected from themonocarboxylic acid compounds that have a structure where the requiredprimary or secondary amino group is not bonded to the same carbon as thecarboxyl group. Examples of compounds having this structure include, butare not limited to, 3,4-diaminobutyric acid and3-amino-5-[(aminoiminomethyl)methylamino]pentanoic acid.

In some embodiments, the second chelating agent can include biguanidegroups. For example, the second chelating agent can have the followingStructure (II):

in which R¹⁰, R¹¹, R¹², and R¹³ are independently selected from thegroup consisting of hydrogen, substituted or unsubstituted aryl,substituted or unsubstituted C₃-C₁₀ cyclic alkyl, and substituted orunsubstituted C₁-C₁₀ linear or branched alkyl; and R¹⁴ is hydrogen or asingle bond that together with R¹³ forms an imidazole ring; providedthat at least one of R¹⁰, R¹¹, R¹², and R¹³ is an aryl group or containsan aryl substituent and that at least two of R¹⁰, R¹¹, R¹², and R¹³ arehydrogen. In some embodiments, R¹¹ and R¹³ are hydrogen. In someembodiments, R¹³ and R¹⁴ are hydrogen.

Examples of suitable aryl groups for R¹⁰-R¹³ include, but are notlimited to phenyl, napthyl, and anthracenyl. Suitable substituentsinclude, but are not limited to halogen (e.g., Cl, Br, or F), C₁-C₁₀linear or branched alkyl, C₃-C₁₀ cyclic alkyl, C₁-C₁₀ linear or branchedalkoxy, C₃-C₁₀ cyclic alkoxy, nitro, SH, dioxolyl, and substituted orunsubstituted phenyl.

Examples of suitable substituted or unsubstituted C₃-C₁₀ cyclic alkylfor R¹⁰-R¹³ include, but are not limited to cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, and bicyclic systems such as norbornyl andfully hydrogenated naphthylene. Suitable substituents included, but arenot limited to, halogen (e.g., Cl, Br, or F), C₁-C₁₀ linear or branchedalkyl, C₃-C₁₀ cyclic alkyl, and substituted or unsubstituted phenyl.

Examples of suitable substituted or unsubstituted C₁-C₁₀ linear orbranched alkyl for R¹⁰-R¹³ include, but are not limited to, methyl,ethyl, propyl, butyl, pentyl, hexyl, octyl, iso-propyl, iso-butyl,t-butyl, 1,1,2,2-tetramethylpropyl, and decyl. Suitable substituentsinclude, but are not limited to, halogen (e.g., Cl, Br, or F), C₁-C₁₀linear or branched alkoxy, C₁-C₁₀ linear or branched fluoroalkoxy,C₃-C₁₀ cyclic alkoxy, and substituted or unsubstituted aryl.

Examples of biguanides having a substituted or unsubstituted arylinclude, but are not limited to, 1-phenylbiguanide,1-(o-tolyl)biguanide, 1-(3-methylphenyl)biguanide,1-(4-methylphenyl)biguanide, 1-(2-chlorophenyl)biguanide,1-(4-chlorophenyl)biguanide, 1-(2,3-dimethylphenyl)biguanide,1-(2,6-dimethylphenyl)biguanide, 1-(1-naphthyl)biguanide,1-(4-methoxyphenyl)biguanide, 1-(4-nitrophenyl)biguanide,1,1-diphenylbiguanide, 1,5-diphenylbiguanide,1,5-bis(4-chlorophenyl)biguanide, 1,5-bis(3-chlorophenyl)biguanide,1-(4-chloro)phenyl-5-(4-methoxy)phenylbiguanide,1,1-bis(3-chloro-4-methoxyphenyl)biguanide,1,5-bis(3,4-dichlorophenyl)biguanide,1,5-bis(3,5-dichlorophenyl)biguanide, 1,5-bis(4-bromophenyl)biguanide.

Examples of biguanides having a substituted or unsubstituted aryl groupand a substituted or unsubstituted C₁-C₁₀ linear or branched alkyl groupinclude, but are not limited to, 1-phenyl-1-methylbiguanide,1-(4-chlorophenyl)-5-(1-methylethyl)biguanide (Proguanil),1-(3,4-dichlorophenyl)-5-(1-methylethyl)biguanide,1-(4-methylphenyl)-5-octylbiguanide,1-(4-chlorophenyl)-2-(N′-propan-2-ylcarbamimidoyl) guanidine,ditolylbiguanide, dinaphthylbiguanide, and dibenzylbiguanide.

Examples of biguanides having a substituted or substituted C₁-C₁₀ linearor branched alkyl include, but are not limited to, 4-chlorobenzhydrylbiguanide, 1-benzo[1,3]dioxol-5-ylmethylbiguanide,1-benzyl-5-(pyridine-3-yl)methylbiguanide, 1-benzylbiguanide,4-chlorobenzylbiguanide, 1-(2-phenylethyl)biguanide, 1-hexyl-5-benzylbiguanide, 1,1-dibenzylbiguanide, 1,5-dibenzylbiguanide,1-(phenethyl)-5-propylbiguanide, and 1,5-bis(phenethyl)biguanide.

Examples of biguanides having a substituted or unsubstituted C₃-C₁₀cyclic alkyl include, but are not limited to,1-cyclohexyl-5-phenylbiguanide, 1-(4-phenylcyclohexyl)biguanide,1-(4-methyl)cyclohexyl-5-phenylbiguanide, and1-cyclopentyl-5-(4-methoxyphenyl)biguanide, norbornylbiguanide,dinorbornylbiguanide, adamantylbiguanide, diadamantylbiguanide,dicyclohexylbiguanide.

Examples of Structure (II) where R¹⁴ is a single bond that together withR¹³ forms an imidazole ring, include but are not limited to,2-guanidinobenzimidazole, 5-methyl-2-guanidinobenzimidazole,4,6-dimethyl-2-guanidinobenzimidazole,5,6-dimethyl-2-guanidinobenzimidazole,5-chloro-2-guanidinobenzimidazole,4,5-dichloro-2-guanidinobenzimidazole,4,6-dichloro-2-guanidinobenzimidazole, 5-bromo-2-guanidinobenzimidazole,5-phenyl-2-guanidinobenzimidazole, and5-methoxy-2-guanidinobenzimidazole.

In some embodiments, the second chelating agent contains multiplebiguanide groups. In some embodiments, the second chelating agentcontains two biguanide groups. These second chelating agents arereferred to herein as bisbiguanides or dibiguanides. In someembodiments, the second chelating agent containing multiple biguanidegroups is a polymeric biguanide. Polymeric biguanides contemplatedinclude polymers wherein the biguanide moiety is contained within thebackbone of the polymer, as well as polymers containing pendantbiguanide moieties.

An example of the second chelating agent containing two biguanide groupsis a compound of Structure (III):

in which R²⁰, R²¹, R²², and R²³ are independently selected from thegroup consisting of hydrogen, substituted or unsubstituted aryl,substituted or unsubstituted C₃-C₁₀ cyclic alkyl, and substituted orunsubstituted C₁-C₁₀ linear or branched alkyl; each R²⁴ is independentlyselected from the group consisting of hydrogen, substituted orunsubstituted aryl, substituted or unsubstituted phenylethyl, orsubstituted or unsubstituted benzyl alkyl; and m is an integer from 1 to10; provided that at least one of R²⁰, R²¹, R²², R²³ and R²⁴ is an arylgroup or contains an aryl substituent and that at least two of R²⁰, R²¹,R²², and R²³ are hydrogen.

Examples of bisbiguanides of Structure (III) include, but are notlimited to, ethylenedibiguanide, propylenedibiguanide,tetramethylenedibiguanide, pentamethylenedibiguanide,hexamethylenedibiguanide, heptamethylenedibiguanide,octamethylenedibiguanide, 1,6-bis-(4-chlorobenzylbiguanido)-hexane(Fluorhexidine(R)), 1,1′-hexamethylene bis(5-(p-chlorophenyl)biguanide)(chlorhexidine), 2-(benzyloxymethyl)pentane-1,5-bis(5-hexylbiguanide),2-(phenylthiomethyl)pentane-1,5-bis(5-phenethylbiguanide),3-(phenylthio)hexane-1,6-bis(5-hexylbiguanide),3-(phenylthio)hexane-1,6-bis(5-cyclohexylbiguanide),3-(benzylthio)hexane-1,6-bis(5-hexylbiguanide), and3-(benzylthio)hexane-1,6-bis(5-cyclohexylbiguanide).

In one embodiment, the second chelating agent is a bisbiguanide havingthe following structure:

This bisbiguanide is also known as alexidine.

In some embodiments, the second chelating agent containing two biguanidegroups include, but are not limited to, phenylenyldibiguanide,naphthylenyldibiguanide, pyridinyldibiguanide, piperazinyldibiguanide,phthalyldibiguanide, 1,1′-[4-(dodecyloxy)-m-phenylene]bisbiguanide,2-(decylthiomethyl)pentane-1,5-bis(5-isopropylbiguanide), and2-(decylthiomethyl)pentane-1,5-bis(5,5-diethylbiguanide).

In some embodiments, the second chelating agent containing multiplebiguanide groups is a polymeric biguanide. Exemplary polymericbiguanides contemplated as a component of the compositions describedherein have the Structure (IV):

in which n is an integer of at least 2; each R²⁵, independently, is H orC₁-C₆ alkyl; and each R²⁶, independently is optionally substitutedC₁-C₂₀ alkylene (e.g., C₄-C₁₀ alkylene).

As used herein, “alkylene” refers to a divalent organic radical.Examples of divalent alkylene moieties include, but are not limited to,—CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂CH₂—,—CH₂CH₂CH₂CH₂CH₂CH₂—, and the like. In some embodiments, R²⁶ is—CH₂CH₂CH₂CH₂CH₂CH₂—.

In some embodiments, the C₁-C₂₀ alkylene is optionally substituted.Suitable substituents include, but are not limited to, C₁-C₁₀ linear orbranched alkyl, C₃-C₁₀ cyclic alkyl, substituted or unsubstitutedphenyl, C₁-C₁₀ linear or branched alkoxy, C₃-C₁₀ cyclic alkoxy, nitro,hydroxyl, SH, halogen, amino, dioxolyl, biguanidyl, cyano, carboxyl,ester, amide, ether, sulfide, disulfide, sulfoxide, and sulfone.

In some embodiments, at least one methylene unit of the alkylenemoieties described herein is replaced by a heteroatom, such as, —O—,—NH—, —S—, and the like.

In some embodiments, n is an integer from 2 to 6000. In someembodiments, n is an integer from 3 to 3000. In some embodiments, n isan integer from 3 to 1000. In some embodiments, n is an integer from 5to 300. In some embodiments, n is an integer from 5 to 50. In someembodiments, n is an integer from 10 to 20 (e.g., 12 or 15).

In some embodiments, the polymeric biguanides contemplated as componentsin the compositions described herein have the above structure whereinR²⁵ is H, R²⁶ is C₆ alkylene, and n is 12 or 15.

In addition to the polymeric biguanides set forth above, polymericbiguanides bearing pendant biguanide moieties are contemplated. Examplesof these embodiments include, but are not limited to, polymerizationproducts of biguanidyl-substituted α-olefin monomers, such aspoly(vinylbiguanide), poly(N-vinylbiguanide), poly(allylbiguanide), andco-polymers thereof. It is understood that the biguanidyl-substitutedα-olefin monomers can be co-polymerized with a variety of olefinicmonomers, such that the number of pendant biguanidyl moieties perpolymer chain can be varied widely.

The biguanides disclosed herein readily form salts with a variety ofacids, both organic and inorganic. Inorganic acid salts of thebiguanides contemplated for use in the compositions described hereininclude, but are not limited to, hydrochloric, hydrofluoric,hydrobromic, hydroiodic, phosphonic, phosphoric, sulfonic, sulfuric, andthe like. Organic acid salts of the biguanides contemplated for use inthe compositions described herein include, but are not limited to,optionally substituted carboxylic acids such as valeric, hexanoic,octanoic, 2-octenoic, lauric, 5-dodecenoic, myristic, pentadecanoic,palmitic, oleic, stearic, eicosanoic, heptadecanoic, palmitoleic,ricinoleic, 2-hydroxystearic, 6-hydroxyhexadecanoic, 2-hydroxycaproic,2-hydroxydodecanoic, 5-hydroxydodecanoic, 5-hydroxydecanoic,4-hydroxydecanoic, dodecanedioic, undecanedioic, sebacic, benzoic,hydroxbenzoic, teraphthalic, and the like.

Examples of other suitable second chelating agents includealkylenediamines such as ethylenediamine, propylenediamine,butylenediamine, hexylenediamine, diethylenetriamine,triethylenetetramines, and polyethyleneimine having at least 2 nitrogencontaining groups.

In some embodiments, the compositions of this disclosure include atleast about 0.01% by weight (e.g., at least about 0.1% by weight, atleast about 0.2% by weight, at least about 0.3% by weight, or at leastabout 0.4% by weight) and/or at most about 1.8% by weight (e.g., at mostabout 1.5% by weight, at most about 1.3% by weight, at most about 1.1%by weight, at most about 1% by weight, at most about 0.8% by weight, atmost about 0.7% by weight, at most about 0.6% by weight, or at mostabout 0.5% by weight) of the second chelating agent.

The compositions of this disclosure contain at least one metal corrosioninhibitor selected from substituted or unsubstituted benzotriazoles.Suitable classes of substituted benzotriazole include, but are notlimited to, benzotriazoles substituted with alkyl groups, aryl groups,halogen groups, amino groups, nitro groups, alkoxy groups, and hydroxylgroups. Substituted benzotriazoles also include those fused with one ormore aryl (e.g., phenyl) or heteroaryl groups. For the purposes of thisdisclosure, the phrase “substituted or unsubstituted benzotriazoles” isdefined to exclude any benzotriazole compound simultaneously containingboth a carboxyl group and a primary or secondary amino group.

Suitable benzotriazoles for use as a metal corrosion inhibitor include,but are not limited to, benzotriazole (BTA), 5-aminotetrazole,1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole,5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole,4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole,naphthotriazole, tolyltriazole, 5-phenyl-benzotriazole,5-nitrobenzotriazole, 4-nitrobenzotriazole,3-amino-5-mercapto-1,2,4-triazole, 2-(5-amino-pentyl)-benzotriazole,1-amino-benzotriazole, 5-methyl-1H-benzotriazole,benzotriazole-5-carboxylic acid, 4-methylbenzotriazole,4-ethylbenzotriazole, 5-ethylbenzotriazole, 4-propylbenzotriazole,5-propylbenzotriazole, 4-isopropylbenzotriazole,5-isopropylbenzotriazole, 4-n-butylbenzotriazole,5-n-butylbenzotriazole, 4-isobutylbenzotriazole,5-isobutylbenzotriazole, 4-pentylbenzotriazole, 5-pentylbenzotriazole,4-hexylbenzotriazole, 5-hexylbenzotriazole, 5-methoxybenzotriazole,5-hydroxybenzotriazole, dihydroxypropylbenzotriazole,1-[N,N-bis(2-ethylhexyl)aminomethyl]-benzotriazole, 5-t-butylbenzotriazole, 5-(1′,1′-dimethylpropyl)-benzotriazole,5-(1′,1′,3′-trimethylbutyl)benzotriazole, 5-n-octyl benzotriazole, and5-(1′,1′,3′,3′-tetramethylbutyl)benzotriazole.

In some embodiments, the compositions of this disclosure include atleast about 0.05% by weight (e.g., at least about 0.1% by weight, atleast about 0.2% by weight, or at least about 0.3% by weight) and/or atmost about 1% by weight (e.g., at most about 0.7% by weight, at mostabout 0.6% by weight, or at most about 0.5% by weight) of the metalcorrosion inhibitor.

The compositions of this disclosure contain at least one organic solventselected from the group of water soluble alcohols, water solubleketones, water soluble esters, and water soluble ethers (e.g., glycoldiethers).

Classes of water soluble alcohols include, but are not limited to,alkane diols (including, but not limited to, alkylene glycols), glycols,alkoxyalcohols (including but not limited to glycol monoethers),saturated aliphatic monohydric alcohols, unsaturated non-aromaticmonohydric alcohols, and low molecular weight alcohols containing a ringstructure.

Examples of water soluble alkane diols includes, but are not limited to,2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol,1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol,and alkylene glycols.

Examples of water soluble alkylene glycols include, but are not limitedto, ethylene glycol, propylene glycol, diethylene glycol, dipropyleneglycol, triethylene glycol and tetraethyleneglycol.

Examples of water soluble alkoxyalcohols include, but are not limitedto, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol,1-methoxy-2-butanol, and water soluble glycol monoethers.

Examples of water soluble glycol monoethers include, but are not limitedto, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,ethylene glycol mono n-propyl ether, ethylene glycol monoisopropylether, ethylene glycol mono n-butyl ether, diethylene glycol monomethylether, diethylene glycol monoethyl ether, diethylene glycolmonobutylether, triethylene glycol monomethyl ether, triethylene glycolmonoethyl ether, triethylene glycol monobutyl ether,1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol,2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropyleneglycol monomethyl ether, dipropylene glycol monoethyl ether, dipropyleneglycol mono-n-propyl ether, tripropylene glycol monoethyl ether,tripropylene glycol monomethyl ether and ethylene glycol monobenzylether, diethylene glycol monobenzyl ether.

Examples of water soluble saturated aliphatic monohydric alcoholsinclude, but are not limited to methanol, ethanol, n-propyl alcohol,isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butylalcohol, 2-pentanol, t-pentyl alcohol, and 1-hexanol.

Examples of water soluble unsaturated non-aromatic monohydric alcoholsinclude, but are not limited to allyl alcohol, propargyl alcohol,2-butenyl alcohol, 3-butenyl alcohol, and 4-penten-2-ol.

Examples of water soluble, low molecular weight alcohols containing aring structure include, but are not limited, to tetrahydrofurfurylalcohol, furfuryl alcohol, and 1,3-cyclopentanediol.

Examples of water soluble ketones include, but are not limited to,acetone, propanone, cyclobutanone, cyclopentanone, cyclohexanone,diacetone alcohol, 2-butanone, 5-hexanedione, 1,4-cyclohexanedione,3-hydroxyacetophenone, 1,3-cyclohexanedione, and cyclohexanone.

Examples of water soluble esters include, but are not limited to, ethylacetate, glycol monoesters such as ethylene glycol monoacetate,diethyleneglycol monoacetate, and glycol monoether monoesters such aspropylene glycol monomethyl ether acetate, ethylene glycol monomethylether acetate, propylene glycol monoethyl ether acetate, and ethyleneglycol monoethylether acetate.

In some embodiments, the compositions of this disclosure include atleast about 1% by weight (e.g., at least about 5% by weight, at leastabout 8% by weight, or at least about 10% by weight) and/or at mostabout 30% by weight (e.g., at most about 25% by weight, at most about20% by weight, or at most about 15% by weight) of the organic solvent.

The cleaning compositions of the present disclosure further includewater. Preferably, the water is de-ionized and ultra-pure, contains noorganic contaminants and has a minimum resistivity of about 4 to about17 mega Ohms. More preferably, the resistivity of the water is at least17 mega Ohms.

In some embodiments, the compositions of this disclosure include atleast about 78% by weight (e.g., at least about 80% by weight, at leastabout 83% by weight, or at least about 85% by weight) and/or at mostabout 98% by weight (e.g., at most about 95% by weight, at most about93% by weight, or at most about 90% by weight) of water.

The compositions of this disclosure optionally contains at least one pHadjusting agent to control the pH to between about 6 to about 11. Insome embodiments, the compositions of this disclosure can have a pH ofat least about 6 (e.g., at least about 6.5, at least about 7, or atleast about 7.5) to at most about 11 (e.g., at most about 10, at mostabout 9.5, at most about 9, at most about 8.5). Without wishing to bebound by theory, it is believed that a cleaning composition having a pHhigher than 11 decreases the plasma etch residue cleaning to animpractical level for complete cleaning and that a pH lower than 6 wouldincrease the etch rate of W to an undesirable level. The effective pHcan vary depending on the types and amounts of the ingredients used inthe compositions described herein.

The amount of pH adjusting agent required, if any, can vary as theconcentration of the other components is varied in differentformulations, particularly the hydroxylamine, the first chelating agentpolyaminopolycarboxylic acid, and the second chelating agent (or itsneutralized salt), and as a function of the molecular weight of theparticular pH adjusting agent employed. In general, the pH adjustingagent concentration ranges from about 0.1% to about 3%. In someembodiments, the cleaning compositions of this disclosure include atleast about 0.1% by weight (e.g., at least about 0.5% by weight, atleast about 1% by weight, or at least about 1.5% by weight) and/or atmost about 3% by weight (e.g., at most about 2.5% by weight, at mostabout 2% by weight, or at most about 1.5% by weight) of the pH adjustingagent.

In general, the pH adjusting agent is free of any metal ion (except fora trace amount of metal ion impurities). Suitable metal ion free pHadjusting agents include ammonium hydroxide, quaternary ammoniumhydroxides, monoamines (including alkanolamines), imines (such as1,8-diazabicyclo[5.4.0]-7-undecene and1,5-diazabicyclo[4.3.0]-5-nonene), and guanidine salts (such asguanidine carbonate).

Examples of suitable quaternary ammonium hydroxides, include, but arenot limited to, tetramethyl ammonium hydroxide, tetraethyl ammoniumhydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammoniumhydroxide, dimethyldiethylammonium hydroxide, choline,tetraethanolammonium hydroxide, benzyltrimethylammonium hydroxide,benzyltriethylammonium hydroxide, and benzyltributylammonium hydroxide.

Examples of suitable monoamines include, but are not limited to,triethylamine, tributylamine, tripentylamine, ethanolamine,diethanolamine, diethylamine, butylamine, dibutylamine, and benzylamine.

In some embodiments, the non-corrosive cleaning composition of thisdisclosure contains, consists, or consists essentially of at least about0.5% by weight (e.g., at least about 1% by weight, at least about 2% byweight, at least about 3% by weight, or at least about 5% by weight)and/or at most about 20% by weight (e.g., at most about 17% by weight,at most about 15% by weight, at most about 12% by weight, or at mostabout 10% by weight) of the redox agent; at least about 0.01% by weight(e.g., at least about 0.1% by weight, at least about 0.2% by weight orat least about 0.3% by weight) and/or at most about 1% by weight (e.g.,at most about 0.7% by weight, at most about 0.6% by weight or at mostabout 0.5% by weight) of the first chelating agent (i.e., apolyaminopolycarboxylic acid); at least about 0.01% by weight (e.g., atleast about 0.1% by weight, at least about 0.2% by weight, at leastabout 0.3% by weight, or at least about 0.4% by weight) and/or at mostabout 1.8% by weight (e.g., at most about 1.5% by weight, at most about1.3% by weight, at most about 1.1% by weight, at most about 1% byweight, at most about 0.8% by weight, at most about 0.7% by weight, atmost about 0.6% by weight, or at most about 0.5% by weight) of thesecond chelating agent; at least about 0.05% by weight (e.g., at leastabout 0.1% by weight, at least about 0.2% by weight, or at least about0.3% by weight) and/or at most about 1% by weight (e.g., at most about0.7% by weight, at most about 0.6% by weight, or at most about 0.5% byweight) of the metal corrosion inhibitor selected from the groupconsisting of substituted and unsubstituted benzotriazoles; at leastabout 1% by weight (e.g., at least about 5% by weight, at least about 8%by weight, or at least about 10% by weight) and/or at most about 30% byweight (e.g., at most about 25% by weight, at most about 20% by weight,or at most about 15% by weight) of the organic solvent; at least about78% by weight (e.g., at least about 80% by weight, at least about 83% byweight, or at least about 85% by weight) and/or at most about 98% byweight (e.g., at most about 95% by weight, at most about 93% by weight,or at most about 90% by weight) of water; and optionally, about 0.1% toabout 3% of a metal ion free pH adjusting agent; wherein the pH of thenon-corrosive cleaning composition is from at least 6 (e.g., at leastabout 6.5, at least about 7, or at least about 7.5) to at most about 11(e.g., at most about 10, at most about 9.5, at most about 9, at mostabout 8.5).

In some embodiments, the non-corrosive cleaning composition of thisdisclosure contains, consists, or consists essentially of at least about0.5% by weight (e.g., at least about 1% by weight, at least about 2% byweight, at least about 3% by weight, or at least about 5% by weight)and/or at most about 20% by weight (e.g., at most about 17% by weight,at most about 15% by weight, at most about 12% by weight, or at mostabout 10% by weight) of hydroxylamine; at least about 0.01% by weight(e.g., at least about 0.1% by weight, at least about 0.2% by weight orat least about 0.3% by weight) and/or at most about 1% by weight (e.g.,at most about 0.7% by weight, at most about 0.6% by weight or at mostabout 0.5% by weight) of the first chelating agent (i.e., apolyaminopolycarboxylic acid); at least about 0.01% by weight (e.g., atleast about 0.1% by weight, at least about 0.2% by weight, at leastabout 0.3% by weight, or at least about 0.4% by weight) and/or at mostabout 1.8% by weight (e.g., at most about 1.5% by weight, at most about1.3% by weight, at most about 1.1% by weight, at most about 1% byweight, at most about 0.8% by weight, at most about 0.7% by weight, atmost about 0.6% by weight, or at most about 0.5% by weight) of thesecond chelating agent selected from the group consisting of compoundshaving at least two nitrogen containing groups selected from the groupconsisting of primary amino, secondary amino, imidazolyl, triazolyl,benzotriazolyl, piperazinyl, pyrolyl, pyrrolidinyl, pyrazolyl,piperidinyl, guanidinyl, biguanidinyl, carbazatyl, hydrazidyl,semicarbazidyl, and aminoguanidinyl; at least about 0.05% by weight(e.g., at least about 0.1% by weight, at least about 0.2% by weight, orat least about 0.3% by weight) and/or at most about 1% by weight (e.g.,at most about 0.7% by weight, at most about 0.6% by weight, or at mostabout 0.5% by weight) of the metal corrosion inhibitor selected from thegroup consisting of substituted and unsubstituted benzotriazoles; atleast about 1% by weight (e.g., at least about 5% by weight, at leastabout 8% by weight, or at least about 10% by weight) and/or at mostabout 30% by weight (e.g., at most about 25% by weight, at most about20% by weight, or at most about 15% by weight) of the organic solventselected from the group consisting of water soluble alcohols, watersoluble ketones, water soluble esters, and water soluble ethers; atleast about 78% by weight (e.g., at least about 80% by weight, at leastabout 83% by weight, or at least about 85% by weight) and/or at mostabout 98% by weight (e.g., at most about 95% by weight, at most about93% by weight, or at most about 90% by weight) of water; and optionally,about 0.1% to about 3% of a metal ion free pH adjusting agent; whereinthe pH of the non-corrosive cleaning composition is from at least 6(e.g., at least about 6.5, at least about 7, or at least about 7.5) toat most about 11 (e.g., at most about 10, at most about 9.5, at mostabout 9, at most about 8.5).

In some embodiments, the non-corrosive cleaning composition of thisdisclosure contains, consists, or consists essentially of at least about0.5% by weight (e.g., at least about 1% by weight, at least about 2% byweight, at least about 3% by weight, or at least about 5% by weight)and/or at most about 20% by weight (e.g., at most about 17% by weight,at most about 15% by weight, at most about 12% by weight, or at mostabout 10% by weight) of hydroxylamine; at least about 0.01% by weight(e.g., at least about 0.1% by weight, at least about 0.2% by weight orat least about 0.3% by weight) and/or at most about 1% by weight (e.g.,at most about 0.7% by weight, at most about 0.6% by weight or at mostabout 0.5% by weight) of the first chelating agent (i.e., apolyaminopolycarboxylic acid); at least about 0.01% by weight (e.g., atleast about 0.1% by weight, at least about 0.2% by weight, at leastabout 0.3% by weight, or at least about 0.4% by weight) and/or at mostabout 1.8% by weight (e.g., at most about 1.5% by weight, at most about1.3% by weight, at most about 1.1% by weight, at most about 1% byweight, at most about 0.8% by weight, at most about 0.7% by weight, atmost about 0.6% by weight, or at most about 0.5% by weight) of thesecond chelating agent selected from the group consisting of amonocarboxylic acid compound containing a primary or secondary aminogroup and at least one additional nitrogen-containing basic group, abiguanide compound having Structure II, and a compound having multiplebiguanide groups; at least about 0.05% by weight (e.g., at least about0.1% by weight, at least about 0.2% by weight, or at least about 0.3% byweight) and/or at most about 1% by weight (e.g., at most about 0.7% byweight, at most about 0.6% by weight, or at most about 0.5% by weight)of the metal corrosion inhibitor selected from the group consisting ofsubstituted and unsubstituted benzotriazoles; at least about 1% byweight (e.g., at least about 5% by weight, at least about 8% by weight,or at least about 10% by weight) and/or at most about 30% by weight(e.g., at most about 25% by weight, at most about 20% by weight, or atmost about 15% by weight) of the organic solvent selected from the groupconsisting of water soluble alcohols, water soluble ketones, watersoluble esters, and water soluble ethers; at least about 78% by weight(e.g., at least about 80% by weight, at least about 83% by weight, or atleast about 85% by weight) and/or at most about 98% by weight (e.g., atmost about 95% by weight, at most about 93% by weight, or at most about90% by weight) of water; and optionally, about 0.1% to about 3% of ametal ion free pH adjusting agent; wherein the pH of the non-corrosivecleaning composition is from at least 6 (e.g., at least about 6.5, atleast about 7, or at least about 7.5) to at most about 11 (e.g., at mostabout 10, at most about 9.5, at most about 9, at most about 8.5).

In addition, in some embodiments, the cleaning compositions of thepresent disclosure may contain additives such as, additional pHadjusting agents, additional corrosion inhibitors, surfactants,additional organic solvents, biocides, and defoaming agents as optionalcomponents.

Examples of suitable defoaming agents include polysiloxane defoamers(e.g., polydimethylsiloxane), polyethylene glycol methyl ether polymers,ethylene oxide/propylene oxide copolymers, and glycidyl ether cappedacetylenic diol ethoxylates (such as those described in U.S. Pat. No.6,717,019, herein incorporated by reference).

In some embodiments, the cleaning compositions of the present disclosuremay specifically exclude one or more of the additive components, in anycombination, if more than one. Such components are selected from thegroup consisting of oxygen scavengers, quaternary ammonium hydroxides,amines, alkali metal and alkaline earth bases (such as NaOH, KOH, LiOH,magnesium hydroxide, and calcium hydroxide), surfactants other than adefoamer, fluoride containing compounds, oxidizing agents (e.g.,peroxides, hydrogen peroxide, ferric nitrate, potassium iodate,potassium permanganate, nitric acid, ammonium chlorite, ammoniumchlorate, ammonium iodate, ammonium perborate, ammonium perchlorate,ammonium periodate, ammonium persulfate, tetramethylammonium chlorite,tetramethylammonium chlorate, tetramethylammonium iodate,tetramethylammonium perborate, tetramethylammonium perchlorate,tetramethylammonium periodate, tetramethylammonium persulfate, ureahydrogen peroxide, and peracetic acid), abrasives, silicates,hydroxycarboxylic acids, carboxylic and polycarboxylic acids lackingamino groups, non-azole corrosion inhibitors, guanidine, guanidinesalts, inorganic acids (e.g., sulfonic acids, sulfuric acid, sulfurousacid, nitrous acid, nitric acid, phosphorous acid, and phosphoric acid),pyrrolidone, polyvinyl pyrrolidone, metal halides, metal halides of theformula W_(z)MX_(y), wherein W is selected from H, an alkali or alkalineearth metal, and a metal-ion-free hydroxide base moiety; M is a metalselected from the group consisting of Si, Ge, Sn, Pt, P, B, Au, Ir, Os,Cr, Ti, Zr, Rh, Ru and Sb; y is from 4 to 6; and z is 1, 2, or 3, andcorrosion inhibitors other than those described in this disclosure.

In general, the cleaning compositions of the present disclosure are notspecifically designed to remove bulk photoresist films fromsemiconductor substrates. Rather, the cleaning compositions of thepresent disclosure are generally designed to remove all residues afterbulk resist removal by dry or wet stripping methods. Therefore, thecleaning method of the present disclosure is preferably employed after adry or wet photoresist stripping process. This photoresist strippingprocess is generally preceded by a pattern transfer process, such as anetch or implant process, or it is done to correct mask errors beforepattern transfer. The chemical makeup of the residue will depend on theprocess or processes preceding the cleaning step.

Any suitable dry stripping process can be used to remove bulk resistfrom semiconductor substrates. Examples of suitable dry strippingprocesses include oxygen based plasma ashing, such as a fluorine/oxygenplasma or a N₂/H₂ plasma; ozone gas phase-treatment; fluorine plasmatreatment, hot H₂ gas treatment (such as that described in U.S. Pat. No.5,691,117 incorporated herein by reference in its entirety), and thelike. In addition, any conventional organic wet stripping solution knownto a person skilled in the art can be used to remove bulk resist fromsemiconductor substrates.

A preferred stripping process used in combination with the cleaningmethod of the present disclosure is a dry stripping process. Preferably,this dry stripping process is the oxygen based plasma ashing process.This process removes most of the photoresist from the semiconductorsubstrate by applying a reactive-oxygen atmosphere at elevatedtemperatures (typically 250° C.) at vacuum conditions (i.e., 1 torr).Organic materials are oxidized by this process and are removed with theprocess gas. However, this process does not remove inorganic ororganometallic contamination from the semiconductor substrate. Asubsequent cleaning of the semiconductor substrate with the cleaningcomposition of the present disclosure is typically necessary to removethose residues.

One embodiment of the present disclosure is a method of cleaningresidues from a semiconductor substrate that includes contacting asemiconductor substrate containing post etch residues and/or post ashresidues with a cleaning composition described herein. The method canfurther include rinsing the semiconductor substrate with a rinse solventafter the contacting step and/or drying the semiconductor substrateafter the rinsing step.

In some embodiments, the cleaning method include the steps of:

-   -   (A) providing a semiconductor substrate containing post etch        and/or post ash residues;    -   (B) contacting said semiconductor substrate with a cleaning        composition described herein;    -   (C) rinsing said semiconductor substrate with a suitable rinse        solvent; and    -   (D) optionally, drying said semiconductor substrate by any means        that removes the rinse solvent and does not compromise the        integrity of said semiconductor substrate.        In some embodiments, the cleaning method further includes        forming a semiconductor device (e.g., an integrated circuit        device such as a semiconductor chip) from the semiconductor        substrate obtained by the method described above.

The semiconductor substrates to be cleaned in this method can containorganic and organometallic residues, and additionally, a range of metaloxides that need to be removed. Semiconductor substrates typically areconstructed of silicon, silicon germanium, Group III-V compounds likeGaAs, or any combination thereof. The semiconductor substrates mayadditionally contain exposed integrated circuit structures such asinterconnect features like metal lines and dielectric materials. Metalsand metal alloys used for interconnect features include, but are notlimited to, aluminum, aluminum alloyed with copper, copper, titanium,tantalum, cobalt, and silicon, titanium nitride, tantalum nitride, andtungsten. Said semiconductor substrate may also contain layers ofinterlayer dielectrics, silicon oxide, silicon nitride, silicon carbide,titanium oxide, and carbon doped silicon oxides.

The semiconductor substrate can be contacted with a cleaning compositionby any suitable method, such as placing the cleaning composition into atank and immersing and/or submerging the semiconductor substrates intothe cleaning composition, spraying the cleaning composition onto thesemiconductor substrate, streaming the cleaning composition onto thesemiconductor substrate, or any combinations thereof. Preferably, thesemiconductor substrates are immersed into the cleaning composition.

The cleaning compositions of the present disclosure may be effectivelyused up to a temperature of about 90° C. Preferably, the cleaningcompositions can be used from about 25° C. to about 80° C. Morepreferably, the cleaning compositions can be employed in the temperaturerange from about 30° C. to about 60° C. and most preferred is atemperature range of about 40° C. to about 60° C.

Similarly, cleaning times can vary over a wide range depending on theparticular cleaning method and temperature employed. When cleaning in animmersion batch type process, a suitable time range is, for example, upto about 60 minutes. A preferred range for a batch type process is fromabout 1 minute to about 60 minutes. A more preferred time range for abatch type process is from about 3 minutes to about 20 minutes. A mostpreferred time range for a batch type cleaning process is from about 4minutes to about 15 minutes.

Cleaning times for a single wafer process may range from about 10seconds to about 5 minutes. A preferred cleaning time for a single waferprocess may range from about 15 seconds to about 4 minutes. A morepreferred cleaning time for a single wafer process may range from about15 seconds to about 3 minutes. A most preferred cleaning time for asingle wafer process may range from about 20 seconds to about 2 minutes.

To further promote the cleaning ability of the cleaning composition ofthe present disclosure, mechanical agitation means may be employed.Examples of suitable agitation means include circulation of the cleaningcomposition over the substrate, streaming or spraying the cleaningcomposition over the substrate, and ultrasonic or megasonic agitationduring the cleaning process. The orientation of the semiconductorsubstrate relative to the ground may be at any angle. Horizontal orvertical orientations are preferred.

The cleaning compositions of the present disclosure can be used inconventional cleaning tools known to those skilled in the art. Asignificant advantage of the compositions of the present disclosure isthat they include relatively non-toxic, non-corrosive, and non-reactivecomponents in whole and in part, whereby the compositions are stable ina wide range of temperatures and process times. The compositions of thepresent disclosure are chemically compatible with practically allmaterials used to construct existing and proposed semiconductor wafercleaning process tools for batch and single wafer cleaning.

Subsequent to the cleaning, the semiconductor substrate is rinsed with asuitable rinse solvent for about 5 seconds up to about 5 minutes with orwithout agitation means. Examples of suitable rinse solvents include,but are not limited to, deionized (DI) water, methanol, ethanol,isopropyl alcohol, N-methylpyrrolidinone, gamma-butyrolactone, dimethylsulfoxide, ethyl lactate and propylene glycol monomethyl ether acetate.Alternatively, aqueous rinses with pH>8 (such as dilute aqueous ammoniumhydroxide) may be employed. Preferred examples of rinse solventsinclude, but are not limited to, dilute aqueous ammonium hydroxide, DIwater, methanol, ethanol and isopropyl alcohol. More preferred rinsesolvents are dilute aqueous ammonium hydroxide, DI water and isopropylalcohol. The most preferred rinse solvents are dilute aqueous ammoniumhydroxide and DI water. The solvent may be applied using means similarto that used in applying a cleaning composition described herein. Thecleaning composition may have been removed from the semiconductorsubstrate prior to the start of the rinsing step or it may still be incontact with the semiconductor substrate at the start of the rinsingstep. Preferably, the temperature employed in the rinsing step isbetween 16° C. and 27° C.

Optionally, the semiconductor substrate is dried after the rinsing step.Any suitable drying means known in the art may be employed. Examples ofsuitable drying means include spin drying, flowing a dry gas across thesemiconductor substrate, or heating the semiconductor substrate with aheating means such as a hotplate or infrared lamp, Maragoni Marangonidrying, rotagoni drying, IPA drying or any combinations thereof. Dryingtimes will be dependent on the specific method employed but aretypically on the order of 30 seconds up to several minutes.

In some embodiments, a method of manufacturing an integrated deviceusing a cleaning composition described herein can include the followingsteps. First, a layer of a photoresist is applied to a semiconductorsubstrate. The semiconductor substrate thus obtained can then undergo apattern transfer process, such as an etch or implant process, to form anintegrated circuit. The bulk of the photoresist can then be removed by adry or wet stripping method (e.g., an oxygen based plasma ashingprocess). Remaining residues on the semiconductor substrate can then beremoved using a cleaning composition described herein in the mannerdescribed above. The semiconductor substrate can subsequently beprocessed to form one or more additional circuits on the substrate orcan be processed to form into a semiconductor chip by, for example,assembling (e.g., dicing and bonding) and packaging (e.g., chipsealing).

EXAMPLES

The present disclosure is illustrated in more detail with reference tothe following examples, which are for illustrative purposes and shouldnot be construed as limiting the scope of the present disclosure. Anypercentages listed are by weight (wt %) unless otherwise specified.Controlled stirring during testing was done with a 1 inch stirring barat 300 rpm unless otherwise noted.

General Procedure 1 Formulation Blending

Samples of cleaning compositions were prepared by adding, whilestirring, to the calculated amount of ultra-pure deionized water (DIW)the components of the cleaning formulation except for the metal ion freepH adjuster. After a uniform solution was achieved, the optionaladditives, if used, were added. Formulation of the composition wascompleted by the addition of the pH adjuster. The solution was allowedto equilibrate and the pH of the cleaning composition was taken, ifdesired.

The pH measurements, if desired, were taken at ambient temperature(17-25° C.) after all components were fully dissolved. Beckman Coulter Φ400 Series Handheld meters can be used for these pH measurements. Allcomponents used were commercially available and of high purity.

General Procedure 2 Cleaning Evaluation with Beaker Test

The cleaning of PER (Post Etch Residue) from a substrate was carried outwith the described cleaning compositions using a multilayered substrateof Photoresist/TiOx/SiN/Co/ILD (ILD=Inter Layer Dielectric) orphotoresist/TiOx/SiN/W/ILD that had been patterned lithographically,etched in a plasma metal etcher, and followed by oxygen plasma ashing toremove the top layer of photoresist completely.

The test coupons were held using 4″ long plastic locking tweezers,whereby the coupon could then be suspended into a 500 ml volume glassbeaker containing approximately 200 milliliters of the cleaningcompositions of the present disclosure. Prior to immersion of the couponinto the cleaning composition, the composition was pre-heated to thedesired test condition temperature (typically 40° C. or 60° C. as noted)with controlled stirring. The cleaning tests were then carried out byplacing the coupon which was held by the plastic tweezers into theheated composition in such a way that the PER layer containing side ofthe coupon faced the stir bar. The coupon was left static in thecleaning composition for a time period (typically 2 to 5 minutes) whilethe composition was kept at the test temperature under controlledstirring. When the desired cleaning time was completed, the coupon wasquickly removed from the cleaning composition and placed in a 500 mlplastic beaker filled with approximately 400 ml of DI water at ambienttemperature (˜17° C.) with gentle stirring. The coupon was left in thebeaker of DI water for approximately 30 seconds, and then quicklyremoved, and rinsed under a DI water stream at ambient temperature forabout 30 seconds. The coupon was immediately exposed to a nitrogen gasstream from a hand held nitrogen blowing gun, which caused any dropletson the coupon surface to be blown off the coupon, and further, tocompletely dry the coupon device surface. Following this final nitrogendrying step, the coupon was removed from the plastic tweezers holder andplaced into a covered plastic carrier with the device side up for shortterm storage no greater than about 2 hours. The scanning electronmicroscopy (SEM) images were then collected for key features on thecleaned test coupon device surface.

General Procedure 3 Materials Compatibility Evaluation with Beaker Test

The blanket Co on silicon substrate, W on silicon substrate, TiOx onSiO₂ on silicon substrate, SiN on silicon substrate, ILD on siliconsubstrate were diced into approximately 1 inch×1 inch square testcoupons for the materials compatibility tests. The test coupons wereinitially measured for thickness or sheet resistance by the 4-pointprobe, CDE Resmap 273 for metallic film (Co, W), or by Elipsometry fordielectric film (TiOx, SiN and ILD) using a Woollam M-2000X. The testcoupons were then installed on the 4″ long plastic locking tweezers andtreated as described in the cleaning procedure in General Procedure 3with the Co, W, TiOx, SiN, or ILD layer containing side of the couponfaced the stir bar for 10 minutes.

After the final nitrogen drying step, the coupon was removed from theplastic tweezers holder and placed into a covered plastic carrier. Thepost-thickness or sheet resistance was then collected on thepost-processing test coupon surface by the 4-point probe, CDE Resmap 273for metallic film (Co and W) or by Elipsometry for dielectric film(TiOx, SiN and ILD) using a Woollam M-2000X.

Formulation Examples FE-1-FE-5 and Comparative Formulation ExamplesCFE-1-CFE-4

Table 1 contains formulations FE-1-FE-5 and comparative formulationsCFE-1- CFH-4 prepared by General Procedure 1.

TABLE 1 Polyamino- Hydroxyl- polycarboxylic Second Corr. Org. pH Ex.H₂O₂ amine acid Chelant Inhib. Solvent Water adjuster pH FE-1 none 4.00%DTPA (0.5%) CDC 5MBTA EGBE 90.25% none 6.83 (0.001%) (0.25%) (5%) FE-2none 4.00% DTPA (0.5%) CDC 5MBTA EGBE 89.75% DBU 7.47 (0.001%) (0.25%)(5%) (0.5%)  FE-3 none 4.00% DTPA (0.5%) CDC 5MBTA EGBE 89.32% DBU 8.49(0.001%) (0.25%) (5%) (0.93%) FE-4 none 4.00% DTPA (0.5%) CDC 5MBTA EGBE88.96% DBU 9.01 (0.001%) (0.25%) (5%) (1.04%) CFE-1 none 4.00% DTPA(0.5%) CDC 5MBTA EGBE 89.11% DBU 9.6 (0.001%) (0.25%) (5%) (1.14%) CFE-2none 4.00% DTPA (0.5%) CDC 5MBTA EGBE 88.97% DBU 10.2 (0.001%) (0.25%)(5%) (1.28%) FE-5 none 4.00% DTPA (0.5%) Arginine 5MBTA EGBE 89.16% DBU8.47 (0.25%)  (0.25%) (5%) (0.85%) CFE-3 none 4.00% DTPA (0.5%) none5MBTA EGBE 89.29% DBU 8.53 (0.25%) (5%) (0.97%) CFE-4 5% none  DTPA(0.25%) none 5MBTA EGBE 83.98% DBU 7.9 (0.22%) (10%)  (0.55%) EGBE =ethylene glycol butyl ether; DTPA = diethylenetriamine pentaacetic acid;5MBTA = 5-methylbenzotriazole; DBU =.1,8-diazabicyclo[5.4.0]undec-7-ene; CDC = chlorhexidine dihydrochlorideArginine =

Examples 1-5 and Comparative Examples CE1-CE4 Compatability of Cleanerswith Exposed Metals

Formulation Examples FE-1-FE-5 and Comparative Formulation ExamplesCFE-1-CFE-4 were tested for cleaning according to General Procedure 2and for materials compatibility according to General Procedure 3 at 65°C. for 4 minutes. The etch rates (Angstroms/minute) of Co, W, TiOx, SiN,SiC, TEOS (tetraethyl-orthosilicate), and ILD in the cleaningcompositions are shown in Table 2.

TABLE 2 Formulation Clean Example Example TiOx W Co ILD SiN SiC TEOS (4min.) 1 FE-1 1.6 2.1 0.2 NA NA NA NA clean 2 FE-2 1.9 1.2 0.1 NA NA NANA clean 3 FE-3 2.2 1.1 0.1 0.4 0.1 0.3 0.8 clean 4 FE-4 1.9 1 0.2 NA NANA NA mostly clean CE-1 CFE-1 0.2 0.7 0.1 NA NA NA NA not clean CE-2CFE-2 0.1 0.4 0.1 NA NA NA NA not clean 5 FE-5 2.4 4.3 0.1 0.4 0.3 0.30.7 clean CE-3 CFE-3 2.7 5.2 0.1 0.5 0.1 0   0.7 clean CE-4 CFE-43.6 >200 0.2 0.2 NA NA NA clean “NA” refers to data not available.

The data in Table 2 show that formulations of this disclosure (i.e.,FE-1-FE-5) cleaned the post etch residue without significantly etchingthe semiconductor materials (such as Co, W, TiOx, SiN, SiC, TEOS, andILD) typically found in semiconductor devices. On the other hand,Comparative Formulations CFE-1 and CFE-2 that had a pH above 9.5resulted in poor cleaning. In addition, comparative formulation CFE-3that had no second chelating agent exhibited significant etching oftungsten in the tested semiconductor substrate. Similarly, comparativeformulation CFE-4 that included hydrogen peroxide instead ofhydroxylamine also exhibited significant etching of tungsten in thesemiconductor substrate.

Formulation Examples FE-6-FE-13 and Comparative Formulation ExamplesCFE-5 and CFE-6

Table 3 details formulations FE-6-FE-13 and Comparative FormulationsCFE-5 and CFE-6, which were prepared by General Procedure 1.

TABLE 3 Polyamino- Formulation Hydroxyl polycarboxylic Second Corr.Organic pH Example amine acid Chelant Inhib. Solvent Water adjuster pHCFE-5 5.5% HA 0.50% DTPA none 0.25% 5% 87.86% 0.89% 8.68 5MBTA EGBE DBUFE-6  5.5% HA 0.50% DTPA 0.75% 0.25% 5% 87.84% 0.16% 8.52 PBG 5MBTA EGBEDBU FE-7  5.5% HA 0.50% DTPA 1.08% 0.25% 5% 87.67% None 8.47 PBG 5MBTAEGBE FE-8  5.5% HA 0.50% DTPA 0.75% 0.25% 5% 86.75% 1.25% 10.72 PBG5MBTA EGBE DBU FE-9  5.5% HA 0.50% DTPA 1.47% 0.25% 5% 85.58% 1.45% 8.60PFCl 5MBTA EGBE DBU CFE-6 5.5% HA 0.50% DTPA 1.01% 0.25% 5% 86.79% 0.95%8.55 MTCl 5MBTA EGBE DBU FE-10 6.25% HA  0.50% DTPA 0.95% 0.25% 5%87.05% None 8.45 TBG 5MBTA EGBE FE-11 5.5% HA 0.50% DTPA 1.17% 0.25% 5%87.58% None 8.54 TBG 5MBTA EGBE FE-12 5.5% HA 0.50% DTPA 1.30% 0.25% 5%87.45% None 9.13 TBG 5MBTA EGBE FE-13 5.5% HA 0.50% DTPA 0.25% 0.25% 5%87.64% 0.86% 8.54 GBI 5MBTA EGBE DBU

Phenylbiguanide (PBG)

1-(o-Tolyl)biguanide (TBG)

Phenformin hydrochloride (PFCl)

Metformin hydrochloride (MTCl)

2-Guanidinobenzimidazole (GBI)

Examples 6-13 and Comparative Examples CE-5 and CE-6 Compatability ofCleaners with Exposed Metals

Formulation Examples FE-6-FE-13 and Comparative Formulation ExamplesCFE-5 and CFE-6 were tested for cleaning ability according to GeneralProcedure 2 and for materials compatibility according to GeneralProcedure 3 at 65° C. for 4 minutes. The etch rates (Angstroms/minute)of Co, W, TiOx, SiN, SiC, and ILD (where available) for the cleaningcompositions are shown in Table 4.

All formulations in Table 4 showed excellent cleaning ability. However,Comparative Formulations CFE-5 (no biguanide) and CFE-6 (dialkylbiguanide) showed unacceptably high W etch rates. Formulation ExamplesFE-6-FE13 showed significantly decreased W etch rates, while maintainingacceptable etch rates on other materials and having excellent cleaning.

TABLE 4 Formulation TiOx W Co SiN ILD Example Example [A/min] [A/min][A/min] [A/min] [A/min] Cleaning¹ CE-5 CFE-5 3.4 6.4 NA NA NA 5 6 FE-6 2.9 1.6 NA NA NA 5 7 FE-7  2.7 1.2 0.3 0.8 NA 5 8 FE-8  3.3 2.4 NA NA NA5 9 FE-9  3.2 3.0 0.8 NA NA 5 CE-6 CFE-6 3.5 6.6 0.3 NA NA 5 10 FE-103.2 1.3 0.4 NA NA 5 11 FE-11 3.3 1.2 0.4 0.5 0.4 5 12 FE-12 3.6 1.1 0.6NA NA 5 13 FE-13 3.6 3.3 NA NA NA 5 ¹Rating of 5 is excellent; Rating of1 is very poor. “NA” refers to data not available.

Examples 14-17 and Comparative Examples CE-7 and CE-8 Compatibility ofCleaners with Exposed Metals

Formulation examples FE-14 to FE-17 and comparative formulation examplesCFE-7 and CFE-8 were tested for cleaning ability according to GeneralProcedure 2 and for materials compatibility according to GeneralProcedure 3 at 65° C. for 4 minutes. Table 5 sets forth the cleaningcompositions. “Pol-BG” as set forth in Table 5 refers topolyhexamethylene biguanide, hydrochloride (see the structure below,n=12).

Polyhexamethylene biguanide (Pol-BG), hydrochloride

The etch rates (Angstroms/minute) of Co, W, TiOx, SiN, SiC, and ILD(where available) for the cleaning compositions are shown in Table 6.

TABLE 5 Polyamino- Form Hydroxyl polycarboxylic Second Corr. Organic pHpH Ex. amine acid Chelant Inhib. Solvent H₂O adjuster (65 C.) FE-14 5%0.50% DTPA 0.01% 0.20% EGBE 3% 90.43% 0.763% 7.86 Pol-BG 5MBTA DBU FE-155% 0.70% DTPA 0.01% 0.20% EGBE 4% 89.16% 0.933% 8.00 Pol-BG 5MBTA DBUFE-16 4% 0.60% DTPA 0.01% 0.30% EGBE 4% 90.28% 0.81% 7.9 Pol-BG 5MBTADBU FE-17 5% 0.50% DTPA 0.01% 0.25% EGBE 5% 88.50% 0.74% 8.3 Pol-BG5MBTA DBU CFE-7 5% 0.60% DTPA None 0.20% EGBE 3% 90.44% 0.763% 8.005MBTA DBU CFE-8 4% 0.60% DTPA None 0.25% EGBE 5% 88.50% 0.74% 8.30 5MBTADBU

TABLE 6 Form. TiOx W Co SiN ILD Ex. (A/min) (A/min) (A/min) (A/min)(A/min) Cleaning¹ FE-14 2.1 0.7 0.02 1.4 NA 5 FE-15 1.8 0.7 0.03 1.1 NA5 FE-16 1.2 0.7 0.01 2.3 0.00 5 FE-17 0.9 0.6 0.01 1.5 0.00 4 CFE-7 2.12.4 0.10 0.9 0.00 5 CFE-8 1.9 2.1 0.00 1.2 NA 5 ¹Rating of 5 isexcellent; rating of 1 is very poor. “NA” refers to data not available.

All formulations in Table 6 showed excellent cleaning ability. Howevercomparative formulations CFE-7 and CFE-8 showed unacceptably high W etchrates. Formulation Examples FE-14 to FE17 showed significantly decreasedW etch rates, while maintaining acceptable etch rates on other materialsand having excellent cleaning.

Formulation Examples 18-38

To further elaborate on the compositions of this disclosure, additionalcleaning compositions are described in Table 7. The “second chelant” inTable 7 refers to the polymeric biguanides having Structure (IV) (i.e.,Polymers 1-8 below) or polymeric biguanides containing pendant biguanidegroups (i.e., Polymers 9-12 below). Specifically, Polymers 1-8 are thoseof Structure (IV) in which n, R²⁵ and R²⁶ are defined below.

Polymer # R²⁵ R²⁶ n 1 H C₄-alkylene  10 2 H C₈-alkylene  15 3 HC₁₀-alkylene  20 4 H C₆-alkylene 100 5 H C₆-alkylene 200 6 H C₆-alkylene300 7 H —CH₂CH₂—O—CH₂CH₂—  20 8 H —CH₂CH₂—CH(CO₂H)—CH₂CH₂—   20;Polymers 9-12 are those with pendant biguanide moieties and are listedbelow:

9 polyvinylbiguanide 10 polyallylbiguanide 11 poly(N-vinylbiguanide) 12poly(allylbiguanide-co-allylamine)

TABLE 7 Polyamino- Form. Hydroxyl polycarboxylic Second Corr. OrganicEx. amine acid Chelant Inhib. Solvent H₂O FE-18 5.5% 0.50% DTPA Polymer1 0.25% EGBE 5% 88.74% 0.01% 5MBTA FE-19 5.5% 0.50% DTPA Polymer 2 0.25%EGBE 5% 88.74% 0.01% 5MBTA FE-20 5.5% 0.50% DTPA Polymer 3 0.25% EGBE 5%88.73% 0.02% 5MBTA FE-21 5.5% 0.50% DTPA Polymer 4 0.25% EGBE 5% 88.71%0.04% 5MBTA FE-22 5.5% 0.50% DTPA Polymer 5 0.25% EGBE 5% 88.69% 0.06%5MBTA FE-23 5.5% 0.50% DTPA Polymer 6 0.25% EGBE 5% 88.67% 0.08% 5MBTAFE-24 5.5% 0.50% DTPA Polymer 7 0.25% EGBE 5% 88.65% 0.10% 5MBTA FE-255.5% 0.50% DTPA Polymer 8 0.25% EGBE 5% 88.25% 0.50% 5MBTA FE-26 5.5%0.50% DTPA Polymer 9 0.25% EGBE 5% 87.75% 1.0% 5MBTA FE-27 5.5% 0.50%DTPA Polymer 10 0.25% EGBE 5% 86.95% 1.8% 5MBTA FE-28 5.5% 0.50% DTPAPolymer 11 0.05% 2-ethoxy-1- 91.94% 0.01% BTA propanol 2% FE-29 5.5%0.50% DTPA 1-(4- 0.10% diethylene 83.89% nitrophenyl) 1-hydroxy glycolbiguanide BTA monobutylether 0.01% 10% FE-30 5.5% 0.50% DTPA 1,6-bis-(4-0.40% ethylene glycol 78.59% chlorobenzyl 4-methyl mono n-propylbiguanido)- BTA ether hexane 15% 0.01% FE-31 5.5% 0.50% DTPA alexidine0.50% diethylene 83.49% 0.01% 5-amino glycol tetrazole 10% FE-32 5.5%0.50% DTPA 2,4-diamino- 1.0% 3-methoxy-1- 87.99% butyric acid 4-nitrobutanol 0.01% BTA 5% FE-33 1.0% 0.50% EDTA histidine 0.25% EGBE 5%93.24% 0.01% 5MBTA FE-34 2.5% 0.01% Polymer 12 0.25% EGBE 5% 92.23%diaminopropanol 0.01% 5MBTA tetraacetic acid  FE-35* 7.0% 0.75%1-hexyl-5- 0.25% EGBE 5% 86.49% ethylendiamine benzyl 5MBTA dipropionicacid biguanide 0.01%  FE-36**  10% 1.0% Polymer 1 0.25% EGBE 5% 83.34%ethylendiamine 0.01% 5MBTA diacetic acid FE-37 1.0% 0.50% DTPA butylene0.25% EGBE 5% 93.15% diamine 5MBTA 0.1% FE-38 2.5% 0.40% DTPAtriethylene- 0.25% EGBE 5% 91.35% tetramine 5MBTA 0.5% *Formulation alsocontains 0.5% DBU. **Formulation also contains 0.4% tetramethylammoniumhydroxide (TMAH).

What is claimed is:
 1. A cleaning composition, comprising: 1) at leastone redox agent; 2) at least one first chelating agent, the firstchelating agent being a polyaminopolycarboxylic acid; 3) at least onesecond chelating agent different from the first chelating agent, thesecond chelating agent comprising at least two nitrogen-containinggroups; 4) at least one metal corrosion inhibitor, the metal corrosioninhibitor being a substituted or unsubstituted benzotriazole; 5) atleast one organic solvent selected from the group consisting of watersoluble alcohols, water soluble ketones, water soluble esters, and watersoluble ethers; 6) water; and 7) optionally, at least one pH adjustingagent, the pH adjusting agent being a base free of a metal ion; whereinthe composition is free of a metal halide of the formula W_(z)MX_(y) inwhich W is selected from H, an alkali or alkaline earth metal, and ametal-ion-free hydroxide base moiety; M is a metal selected from thegroup consisting of Si, Ge, Sn, Pt, P, B, Au, Ir, Os, Cr, Ti, Zr, Rh, Ruand Sb; y is from 4 to 6; and z is 1, 2, or
 3. 2. The composition ofclaim 1, wherein the pH of the composition is between 6 and about
 11. 3.The composition of claim 1, wherein the redox agent is hydroxylamine. 4.The composition of claim 1, wherein the composition comprises from about0.5% to about 20% by weight of the redox agent.
 5. The composition ofclaim 1, wherein the polyaminopolycarboxylic acid is selected from thegroup consisting of mono- or polyalkylene polyamine polycarboxylicacids, polyaminoalkane polycarboxylic acids, polyaminoalkanolpolycarboxylic acids, and hydroxyalkylether polyamine polycarboxylicacids.
 6. The composition of claim 1, wherein thepolyaminopolycarboxylic acid is selected from the group consisting ofbutylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,ethylenediaminetetrapropionic acid, triethylenetetraminehexaacetic acid,1,3-diamino-2-hydroxypropane-N,N,N′,N′-tetraacetic acid,propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid,trans-1,2-diaminocyclohexane tetraacetic acid, ethylendiamine diaceticacid, ethylendiamine dipropionic acid,1,6-hexamethylene-diamine-N,N,N′,N′-tetraacetic acid,N,N-bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid,diaminopropane tetraacetic acid, iminodiacetic acid;1,4,7,10-tetraazacyclododecane-tetraacetic acid, diaminopropanoltetraacetic acid, and (hydroxyethyl)ethylenediaminetriacetic acid. 7.The composition of claim 1, wherein the composition comprises from about0.01% to about 1% by weight of the polyaminopolycarboxylic acid.
 8. Thecomposition of claim 1, wherein the second chelating agent is amonocarboxylic acid containing a primary or secondary amino group and atleast one additional basic group containing nitrogen.
 9. The compositionof claim 8, wherein the monocarboxylic acid is a compound of Structure(I):(R³NH)C(R¹)(R²)CO₂H  (I), wherein each of R¹ and R², independently, is ahydrogen atom, C₁-C₄ alkyl, or a group having at least onenitrogen-containing basic group; and R³ is a hydrogen atom, C₁-C₁₀alkyl, or a group having at least one nitrogen-containing basic group;wherein at least one of R¹, R², and R³ is a group having at least onenitrogen-containing basic group.
 10. The composition of claim 9, whereinR¹ is a group having at least one nitrogen-containing basic group, inwhich the group having at least one nitrogen-containing basic group isC₁-C₁₀ alkyl substituted by amino, guanidinyl, or imidazolyl andoptionally further substituted by OH.
 11. The composition of claim 10,wherein R² is H or C₁-C₁₀ alkyl and R³ is H, C₁-C₁₀ alkyl, or a grouphaving at least one nitrogen-containing basic group, in which the grouphaving at least one nitrogen-containing basic group is C₁-C₁₀ alkyloptionally substituted by amino, guanidinyl, or imidazolyl andoptionally further substituted by OH.
 12. The composition of claim 9,wherein R³ is a group having at least one nitrogen-containing basicgroup, in which the group having at least one nitrogen-containing basicgroup is C₁-C₁₀ alkyl substituted by amino, guanidinyl, or imidazolyland optionally further substituted by OH.
 13. The composition of claim12, wherein each of R¹ and R², independently, is H or C₁-C₄ alkyl. 14.The composition of claim 8, wherein the monocarboxylic acid is selectedfrom the group consisting of lysine, 2,3-diaminobutyric acid,2,4-diaminobutyric acid, ornithine, 2,3-diaminopropionic acid,2,6-diaminoheptanoic acid, 4-methyl lysine, 3-methyl lysine,5-hydroxylysine, 3-methyl-L-arginine, arginine, homoarginine,N⁵-monomethyl-L-arginine, N⁵-[imino(methylamino)methyl]-D-ornithine,canavanine, histidine, N-(2-aminoethyl)glycine,N-(2-aminopropyl)glycine, N²-methyllysine, N²-methyl-L-arginine,N²-(2-aminoethyl)-D-arginine, N²-(2-aminoethyl)-L-arginine,2-methyllysine, 2-methyl-L-arginine, 3,4-diaminobutyric acid, and3-amino-5-[(aminoiminomethyl)methylamino] pentanoic acid.
 15. Thecomposition of claim 1, wherein the second chelating agent is a compoundof Structure (II):

in which R¹⁰, R¹¹, R¹², and R¹³ are independently selected from thegroup consisting of hydrogen substituted or unsubstituted aryl,substituted or unsubstituted C₃-C₁₀ cyclic alkyl, and substituted orunsubstituted C₁-C₁₀ linear or branched alkyl; and R¹⁴ is hydrogen or asingle bond that together with R¹³ forms an imidazole ring; providedthat at least one of R¹⁰, R¹¹, R¹² and R¹³ is an aryl group or containsan aryl substituent and that at least two of R¹⁰, R¹¹, R¹² and R¹³ arehydrogen.
 16. The composition of claim 1, wherein the second chelatingagent is a compound of Structure (III):

in which R²⁰, R²¹, R²² and R²³ are independently selected from the groupconsisting of hydrogen, substituted or unsubstituted aryl, substitutedor unsubstituted C₃-C₁₀ cyclic alkyl, and substituted or unsubstitutedC₁-C₁₀ linear or branched alkyl; each R²⁴ is independently selected fromthe group consisting of hydrogen, substituted or unsubstituted aryl,substituted or unsubstituted phenylethyl, or substituted orunsubstituted benzyl alkyl; and m is an integer from 1 to 10; providedthat at least one of R²⁰, R²¹, R²², R²³ and R²⁴ is an aryl group orcontains an aryl substituent and that at least two of R²⁰, R²¹, R²², andR²³ are hydrogen.
 17. The composition of claim 1, where the secondchelating agent is chlorhexidine, an alkylenediamine,diethylenetriamine, triethylenetetramines, or a polyethyleneimine.
 18. Acleaning composition, comprising: 1) at least one redox agent; 2) atleast one first chelating agent, the first chelating agent being apolyaminopolycarboxylic acid; 3) at least one second chelating agentdifferent from the first chelating agent, the second chelating agentcomprising at least two nitrogen-containing groups; 4) at least onemetal corrosion inhibitor, the metal corrosion inhibitor being asubstituted or unsubstituted benzotriazole; 5) at least one organicsolvent selected from the group consisting of water soluble alcohols,water soluble ketones, water soluble esters, and water soluble ethers;6) water; and 7) optionally, at least one pH adjusting agent, the pHadjusting agent being a base free of a metal ion; wherein the secondchelating agent is a polymeric biguanide.
 19. The composition of claim18, wherein the polymeric biguanide is a compound of Structure (IV) or asalt thereof:

wherein: n is an integer of at least 2; each R²⁵, independently, is H orC₁-C₆ alkyl; and R²⁶ is optionally substituted C₁-C₂₀ alkylene.
 20. Thecomposition of claim 19, wherein each R²⁶, independently, is C₄ to C₁₀alkylene.
 21. The composition of claim 19, wherein each R²⁶,independently, is C₆ alkylene.
 22. The composition of claim 19, whereinn is an integer from 5 to
 300. 23. The composition of claim 22, whereinn is an integer from 5 to
 50. 24. The composition of claim 23, wherein nis an integer from 10 to
 20. 25. The composition of claim 24, wherein nis 12 or
 15. 26. The composition of claim 1, wherein the compositioncomprises from about 0.01% to about 1.8% by weight of the secondchelating agent.
 27. The composition of claim 1, wherein the metalcorrosion inhibitor is benzotriazole optionally substituted by at leastone substituent selected from the group consisting of alkyl groups, arylgroups, halogen groups, amino groups, nitro groups, alkoxy groups, andhydroxyl groups.
 28. The composition of claim 1, wherein the metalcorrosion inhibitor is selected from the group consisting ofbenzotriazole, 5-aminotetrazole, 1-hydroxybenzotriazole,5-phenylthiol-benzotriazole, 5-chlorobenzotriazole,4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole,5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthotriazole,tolyltriazole, 5-phenyl-benzotriazole, 5-nitrobenzotriazole,4-nitrobenzotriazole, 3-amino-5-mercapto-1,2,4-triazole,2-(5-amino-pentyl)-benzotriazole, 1-amino-benzotriazole,5-methyl-1H-benzotriazole, benzotriazole-5-carboxylic acid,4-methylbenzotriazole, 4-ethylbenzotriazole, 5-ethylbenzotriazole,4-propylbenzotriazole, 5-propylbenzotriazole, 4-isopropylbenzotriazole,5-isopropylbenzotriazole, 4-n-butylbenzotriazole,5-n-butylbenzotriazole, 4-isobutylbenzotriazole,5-isobutylbenzotriazole, 4-pentylbenzotriazole, 5-pentylbenzotriazole,4-hexylbenzotriazole, 5-hexylbenzotriazole, 5-methoxybenzotriazole,5-hydroxybenzotriazole, dihydroxypropylbenzotriazole,1-[N,N-bis(2-ethylhexyl)aminomethyl]-benzotriazole, 5-t-butylbenzotriazole, 5-(1′,1′-diimethylpropyl)-benzotriazole,5-(1′,1′,3′-trimethylbutyl)benzotriazole, 5-n-octyl benzotriazole, and5-(1′,1′,3′,3′-tetramethylbutyl)benzotriazole.
 29. The composition ofclaim 1, wherein the composition comprises from about 0.05% to about 1%by weight of the metal corrosion inhibitor.
 30. The composition of claim1, wherein the composition comprises from about 1% to about 30% byweight of the organic solvent.
 31. The composition of claim 1, whereinthe composition comprises from about 78% to about 98% of the water. 32.The composition of claim 1, further comprising at least one pH adjustingagent, the pH adjusting agent being a base free of a metal ion.
 33. Thecomposition of claim 32, wherein the pH adjusting agent is a quaternaryammonium hydroxide, a monoamine, an imine, or a guanidine salt.
 34. Amethod, comprising: contacting a semiconductor substrate containing postetch residues and/or post ash residues with a cleaning composition ofclaim
 1. 35. The method of claim 34, further comprising rinsing thesemiconductor substrate with a rinse solvent after the contacting step.36. The method of claim 35, further comprising drying the semiconductorsubstrate after the rinsing step.
 37. The method of claim 34, furthercomprising forming a semiconductor device from the semiconductorsubstrate.
 38. A cleaning composition, comprising: 1) at least one redoxagent; 2) at least one first chelating agent, the first chelating agentbeing a polyaminopolycarboxylic acid; 3) at least one metal corrosioninhibitor, the metal corrosion inhibitor being a substituted orunsubstituted benzotriazole; 4) at least one organic solvent selectedfrom the group consisting of water soluble alcohols, water solubleketones, water soluble esters, and water soluble ethers; 5) water; and6) optionally, at least one pH adjusting agent, the pH adjusting agentbeing a base free of a metal ion; wherein the composition is free of ametal halide of the formula W_(z)MX_(y) in which W is selected from H,an alkali or alkaline earth metal, and a metal-ion-free hydroxide basemoiety; M is a metal selected from the group consisting of Si, Ge, Sn,Pt, P, B, Au, Ir, Os, Cr, Ti, Zr, Rh, Ru and Sb; y is from 4 to 6; and zis 1, 2, or
 3. 39. The composition of claim 38, wherein the pH of thecomposition is between 6 and about
 11. 40. The composition of claim 38,wherein the redox agent is hydroxylamine.
 41. The composition of claim38, wherein the composition comprises from about 0.5% to about 20% byweight of the redox agent.
 42. The composition of claim 38, wherein thepolyaminopolycarboxylic acid is selected from the ground consisting ofmono- or polyalkylene polyamine polycarboxylic acids, polyaminoalkanepolycarboxylic acids, polyaminoalkanol polycarboxylic acids, andhydroxyalkylether polyamine polycarboxylic acids.
 43. The composition ofclaim 38, wherein the composition comprises from about 0.01% to about 1%by weight of the polyaminopolycarboxylic acid.
 44. The composition ofclaim 38, wherein the metal corrosion inhibitor is benzotriazoleoptionally substituted by at least one substituent selected from thegroup consisting of alkyl groups, aryl groups, halogen groups, aminogroups, nitro groups, alkoxy groups, and hydroxyl groups.
 45. Thecomposition of claim 38, wherein the composition comprises from about0.05% to about 1% by weight of the metal corrosion inhibitor.
 46. Thecomposition of claim 38, further comprising at least one pH adjustingagent, the pH adjusting agent being a base free of a metal ion.
 47. Acleaning composition, comprising hydroxylamine, diethylenetriaminepentaacetic acid, 5-methylbenzotriazole,1,8-diazabicyclo[5.4.0]undec-7-ene, ethylene glycol butyl ether, andwater.
 48. The composition of claim 47, wherein the compositioncomprises: from about 0.5% to about 20% by weight of hydroxylamine; fromabout 0.01% to about 1% by weight of diethylenetriamine pentaaceticacid; from about 0.05% to about 1% by weight of 5-methylbenzotriazole;from about 0.1% to about 3% by weight of1,8-diazabicyclo[5.4.0]undec-7-ene; from about 1% to about 20% by weightof ethylene glycol butyl ether; and from about 78% to about 98% of thewater.